CN101238093B - Process for producing high-purity N-vinylcarboxamides - Google Patents
Process for producing high-purity N-vinylcarboxamides Download PDFInfo
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- CN101238093B CN101238093B CN2006800288648A CN200680028864A CN101238093B CN 101238093 B CN101238093 B CN 101238093B CN 2006800288648 A CN2006800288648 A CN 2006800288648A CN 200680028864 A CN200680028864 A CN 200680028864A CN 101238093 B CN101238093 B CN 101238093B
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- vinylamide
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- vinylcarboxamides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/22—Separation; Purification; Stabilisation; Use of additives
- C07C231/24—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C233/00—Carboxylic acid amides
- C07C233/01—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C233/02—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
- C07C233/04—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C233/05—Carboxylic acid amides having carbon atoms of carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms having nitrogen atoms of carboxamide groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with carbon atoms of carboxamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
Abstract
Disclosed is a process for producing high-purity N-vinylcarboxamides comprising: (A) a step of dissolving a crude N-vinylcarboxamide in an alcohol having 1 to 3 carbon atoms, the crude N-vinylcarboxamide containing 50 to 97% by mass of an N-vinylcarboxamide; (B) a step of adding an aliphatic hydrocarbon having 5 to 10 carbon atoms to the composition obtained in the step (A) to precipitate a crystal of the N-vinylcarboxamide; and (C) a step of separating the crystal of the N-vinylcarboxamide precipitated in the step (B).
Description
The cross reference of related application
The rights and interests of the U.S. provisional application that the application requires to submit on September 22nd, 2005 according to 35U.S.C.119 (e) bar number 60/719,198.
Technical field
The present invention relates to a kind of method for preparing high-purity N-vinylcarboxamides.More specifically, the present invention relates to the inexpensive method that a kind of preparation has the high-purity N-vinylcarboxamides of high polymerizability.
Background technology
As known in the state of the art, the N-vinylamide is to prepare through pyrolysis or catalytic cracking by acid amides, acetaldehyde and pure synthetic N-(1-alkoxyethyl) acid amides.Also known a kind of method, wherein ethylene diamide is synthetic by acid amides and acetaldehyde, and this ethylene diamide is decomposed into acid amides and N-vinylamide.
Before a kind of method obtain containing the N-vinylamide of unreacted material such as acid amides and N-(1-alkoxyethyl-) acid amides.A kind of method in back produces the N-vinylamide and the acid amides of equimolar amount, and this product is the mixture of these compounds.Because the character of N-vinylamide, acid amides and N-(1-alkoxyethyl) acid amides such as boiling point and solubleness are closely similar, from this mixture, separate very difficulty of N-vinylamide.
For head it off, developed many methods and be used for purifying N-vinylamide.Patent documentation 1 discloses and has made water separate the problem that is difficult to separate unreacted material through distillation to solve with aromatic hydrocarbons extraction.Patent documentation 2 discloses through separating with the ORGANIC SOLVENT MIXTURES crystallisation by cooling.Patent documentation 3 discloses with inorganic salt solution and aromatic hydrocarbons and has extracted.
Yet these methods can not prepare the N-vinylamide with sufficiently high purity.
Patent documentation 4 and 5 discloses can prepare through the piezocrystallization purifying has the polymerisable N-vinyl acetamide of highly purified relatively height.
Yet piezocrystallization relates to the substantial contribution investment on equipment, only and if scale operation, be difficult to supply cheaply industrialization product.
Patent documentation 1:JP-A-S61-289069
Patent documentation 2:JP-A-S63-132868
Patent documentation 3:JP-A-H02-188560
Patent documentation 4:JP-A-H07-089916
Patent documentation 5:JP-A-H07-089917
Summary of the invention
The object of the present invention is to provide a kind of cheaply, preparation has the method for high-purity N-vinylcarboxamides of high polymerizability.
The inventor studies to address the above problem by persistence.Thereby found with specific pure and mild specific aliphatic hydrocrbon Processing of Preparation high-purity N-vinylcarboxamides.The present invention is accomplished based on this discovery.
The present invention is summarized as follows.
A kind of method for preparing high purity-N vinylamide, it comprises:
(A) thick N-vinylamide is dissolved in the step in the alcohol with 1-3 carbon atom, this thick N-vinylamide contains the N-vinylamide of 50-97 quality %;
(B) aliphatic hydrocrbon that adding has 5-10 carbon atom in the compsn that in step (A), obtains is to separate out this N-vinylamide crystalline step; With
(C) the N-vinylamide crystalline step of separating out in the separating step (B).
The method that described in [1], prepares high-purity N-vinylcarboxamides wherein in step (A), is dissolved in thick N-vinylamide in 30-100 ℃ the alcohol with 1-3 carbon atom.
The method that described in [1], prepares high-purity N-vinylcarboxamides wherein in step (B), is separated out N-vinylamide crystal under-30 to 40 ℃.
The method that described in [1], prepares high-purity N-vinylcarboxamides wherein in step (C), is passed through filtering separation with N-vinylamide crystal.
Described in [1] or [2], prepare the method for high-purity N-vinylcarboxamides, wherein said alcohol is methyl alcohol.
Described in [1] or [3], prepare the method for high-purity N-vinylcarboxamides, wherein said aliphatic hydrocrbon is normal hexane and/or sherwood oil.
A kind of high-purity N-vinylcarboxamides through each described method preparation in [1]-[6].
A kind of N-vinylamide (being total to) polymkeric substance that comprises the monomer polymerization preparation of the high-purity N-vinylcarboxamides described in [7] through making.
Like each said method for preparing high-purity N-vinylcarboxamides in [1]-[6], wherein said N-vinylamide is the N-vinyl acetamide.
High purity N-vinyl acetamide through the preparation of the method described in [9].
A kind of N-vinyl acetamide (being total to) polymkeric substance that comprises the monomer polymerization preparation of the high purity N-vinyl acetamide described in [10] through making.
The invention effect
Can prepare high-purity N-vinylcarboxamides according to the method for the invention with excellent polymerizability inexpensively.
The best mode of embodiment of the present invention
Below the present invention will be described in further detail.
< method for preparing high-purity N-vinylcarboxamides >
The method of high-purity N-vinylcarboxamides produced according to the present invention is handled thick N-vinylamide with specific pure and mild specific aliphatic hydrocrbon, thereby and obtains the high-purity N-vinylcarboxamides that purity is higher than 97 quality %.
In step (A), the thick N-vinylamide that will contain 50-97 quality %N-vinylamide is dissolved in the alcohol with 1-3 carbon atom.When this thick N-vinylamide comprised the alcohol insoluble matter component in this dissolving step, this alcohol insoluble matter component can be removed through filtering tentatively.
The example of N-vinylamide comprises N-vinyl acetamide, N-vinyl-N-methylacetamide, N-vinyl formamide and N-methyl-N-vinyl formamide.Wherein, preferably N-vinyl acetamide, and method of the present invention can provide and have high purity N-vinyl acetamide that purity is higher than 97 quality %.
Here, said thick N-vinylamide refers to the N-vinylamide that contains impurity.
Said thick N-vinylamide can be through the currently known methods preparation.For example, they can obtain (referring to JP-A-S50-76015) through pyrolysis or the catalytic cracking by acid amides, acetaldehyde and pure synthetic N-(1-alkoxyethyl) acid amides.Perhaps, they can obtain (referring to JP-A-S61-106546) through the pyrolysis by acid amides and acetaldehyde synthetic ethylene diamide.
The example of impurity comprises, still is not limited to especially, and thick N-vinylamide prepares blended unreacted material in the process.Object lesson comprises having 5 or still less alcohol, acid amides, N-(1-alkoxyethyl) acid amides and the ethylene diamide of carbon atom.
This thick N-vinylamide contains 50-97 quality % ideally, is preferably the N-vinylamide of 70-97 quality %.If this N-vinylamide is less than 50 quality %, then the yield of this N-vinylamide is usually lower, and the N-vinylamide that obtains often has low purity and not satisfied polymerizability.
When this thick N-vinylamide contains the N-vinylamide of 50-70 quality %, can make its former state experience method of the present invention.Perhaps, can this bullion be distilled or extracts to improve the concentration of N-vinylamide.Alcohol insoluble matter component in this thick N-vinylamide can be removed through such purifying.The yield of the N-vinylamide that this purifying causes obtaining through the inventive method improves, and all is ideal from purity and polymerizability.
Such as the front discussion in step (A), use alcohol with 1-3 carbon atom.When use had 4 or more a plurality of carbon atoms pure, the N-vinylamide did not often dissolve, and purifying is usually failed.
Example with alcohol of 1-3 carbon atom comprises methyl alcohol, ethanol, n-propyl alcohol and Virahol.These alcohol can use separately or two or more are used in combination.In above-mentioned alcohol, methyl alcohol is preferred.If via the synthetic thick N-vinylamide of N-(1-alkoxyethyl) acid amides, preferably use the alcohol identical to simplify technology with by-product alcohol.
In view of efficient, preferably to allow the minimum amount of this thick N-vinylamide dissolved to use alcohol.The amount of alcohol is preferably the 0.01-2 mass parts, and 0.1-1 mass parts more preferably comprises the thick N-vinylamide of impurity based on 1 mass parts.This consumption of alcohol comprises blended alcohol (if any) in the step of front.When this measured less than said amount, the whole system that crystallization causes comprising impurity was solidified, and usually is impossible thereby separate.When this amount was far longer than said amount, usually separating out of N-vinylamide failed.
Thick N-vinylamide is preferably dissolved in 30-100 ℃, more preferably in 40-100 ℃ the alcohol.The temperature of this scope has increased solubleness and has allowed to reduce the alcohol that uses.Be higher than above-mentioned temperature and can make the sex change of N-vinylamide.
Water can use together with alcohol as required so that in step (B) spontaneously with system separate into alcohol mutually with aliphatic hydrocarbon phase.The amount of water is preferably the 0.1-50 quality % of the total amount of thick N-vinylamide, alcohol and water, more preferably 0.1-30 quality %.When the amount of water surpassed this scope, the N-vinylamide was not usually separated out and often is hydrolyzed.
In preparation method of the present invention, ideally raw material tank, filter vat and product container are purged with nitrogen or dry air atmosphere.Can in this thick N-vinylamide, add small quantity of drying such as sal epsom, prevent that thus the N-vinylamide from absorbing airborne moisture and be hydrolyzed gradually.
In preparation method of the present invention, preferably basic cpd is joined in this thick N-vinylamide in advance, the N-vinylamide is suppressed by acid-hydrolyzed trend in the presence of water thus.
The example of basic cpd comprises sodium salt such as yellow soda ash, sodium hydrogencarbonate, sodium hydroxide, phosphoric acid (hydrogen) sodium and sodium acetate; Sylvite such as salt of wormwood, saleratus, Pottasium Hydroxide, phosphoric acid (hydrogen) potassium and potassium acetate; With aromatic amine such as N-PA, 4; 4 '-two (α, α-Er Jiajibianji) pentanoic, N-phenyl-N '-(1, the 3-dimethylbutyl)-p-phenylenediamine, N-phenyl-N '-sec.-propyl-p-phenylenediamine, N-phenyl-N '-(1-methylheptyl)-p-phenylenediamine, N-phenyl-N '-cyclohexyl-p-phenylenediamine, N; N '-phenylbenzene-p-phenylenediamine, N; N '-two-betanaphthyl-p-phenylenediamine, N, N '-two (1,4-dimethyl-amyl group)-p-phenylenediamine, N; N '-two (l-ethyl-3-methyl amyl)-p-phenylenediamine, N, N '-two (1-methylheptyl)-p-phenylenediamine and N-phenyl-N '-(ptoluene-sulfonyl)-p-phenylenediamine.Wherein, sodium salt is preferred, and more preferably sodium hydrogencarbonate.
Ideally with 1-10,000ppm is preferably 10-1 to basic cpd with respect to thick N-vinylamide, and the amount of 000ppm is used.The amount of inorganic salt surpasses this scope and often causes not exclusively dissolving and will not provide corresponding effects.Under the situation of aromatic amine, its amount surpasses above-mentioned scope and often causes in preparation process aromatic amine not exclusively to be removed, and the N-vinylamide that obtains has low polymerizability.The amount of basic cpd can not provide the effect as stablizer less than said often causing.
In step (B), the aliphatic hydrocrbon that interpolation has 5-10 carbon atom in the compsn that in step (A), obtains is to separate out N-vinylamide crystal.Here, said composition comprises N-vinylamide and the impurity that is dissolved in the alcohol, and alcohol.
Preferred example with aliphatic hydrocrbon of 5-10 carbon atom comprises alkane with 5-10 carbon atom and the naphthenic hydrocarbon with 5-10 carbon atom.Have 4 or still less carbon atom alkane with have 4 or still less the naphthenic hydrocarbon of carbon atom usually be inconvenient because they are gaseous phase at ambient temperature.High boiling, as to have 11 or more a plurality of carbon atoms alkane and the naphthenic hydrocarbon with 11 or more a plurality of carbon atoms often can not be removed after purifying.
Example with alkane of 5-10 carbon atom comprises Skellysolve A, iso-pentane, neopentane; Normal hexane, 2-methylpentane, 3-methylpentane; 2,3-dimethylbutane, 2,2-dimethylbutane; Normal heptane and its isomer; Octane and its isomer; Positive nonane and its isomer; And n-decane and its isomer.
Example with naphthenic hydrocarbon of 5-10 carbon atom comprises pentamethylene; Hexanaphthene, methylcyclopentane; Suberane and its isomer; Cyclooctane and its isomer; Cyclononane and its isomer; And cyclodecane and its isomer.
Aliphatic hydrocrbon can use separately or two or more are used in combination.
In above-mentioned aliphatic hydrocrbon, in view of the viscosity of service temperature aliphatic hydrocarbon phase when it is separated, preferably normal hexane, its isomer and hexanaphthene.Compsn such as sherwood oil are preferred, and the mixture of normal hexane and sherwood oil also is preferred.
The amount of aliphatic hydrocrbon is preferably the 1-50 mass parts, 2-30 mass parts more preferably, the alcohol in the compsn that in step (A), obtains based on 1 mass parts.The amount of aliphatic hydrocrbon is separated out less than the above-mentioned N-vinylamide poor efficiency that often causes.Its amount surpasses above-mentioned scope has often increased not precipitation efficiency.
N-vinylamide crystal, more preferably-20 is separated out under 10 ℃ more preferably-25 to 30 ℃ preferably at-30 to 40 ℃.Usually do not separate out being higher than under the said temperature N-vinylamide.
When this N-vinylamide crystal was separated out, pure and mild aliphatic hydrocrbon was preferably formed two-phase system.When their form two-phase system, be dissolved in the N-vinylamide of alcohol in mutually and in aliphatic hydrocarbon phase, separate out as tabular crystal.When they form two-phase system, the purity of the N-vinylamide that the increase of cooling two phase liquid obtains.
In step (C), with the N-vinylamide crystal separation of separating out in the step (B).
N-vinylamide crystal can separate through evaporating pure and mild aliphatic hydrocrbon.Preferably filter to realize effective separation.
When pure and mild aliphatic hydrocrbon forms two-phase system, can need not to separate alcohol phase and aliphatic hydrocarbon phase through evaporating solvent or through the isolated by filtration crystal.Preferably, separate alcohol mutually and aliphatic hydrocarbon phase and crystal separated from aliphatic hydrocarbon phase.Although the evaporation aliphatic hydrocrbon obtains crystal, it is preferred filtering, because it has removed impurity simultaneously.
Method of the present invention can repeat to improve the purity of N-vinylamide.Resistance polymers matter can be removed through hydrogenization etc.
Alcohol comprises the synthetic middle material that uses of N-vinylamide mutually, like alcohol, acid amides, N-(1-alkoxyethyl) acid amides and ethylene diamide.These materials can reclaim and be reused for the step of the thick N-vinylamide of preparation; For example in N-(1-alkoxyethyl) acid amides synthetic; In ethylene diamide synthetic, and by in N-(1-alkoxyethyl) acid amides or the synthetic N-vinylamide of ethylene diamide.Alcohol mutually in residual N-vinylamide can reclaim through piezocrystallization, crystallisation by cooling or distillation.
< N-vinylamide (being total to) polymkeric substance >
Can be according to N-vinylamide of the present invention (being total to) polymkeric substance through making the monomer polymerization preparation that comprises the high-purity N-vinylcarboxamides that obtains through aforesaid method.Be somebody's turn to do (being total to) polymkeric substance preferably through making the monomer polymerization preparation that comprises the high purity N-vinyl acetamide that obtains by aforesaid method, in other words, be somebody's turn to do preferably N-vinyl acetamide (being total to) polymkeric substance of (being total to) polymkeric substance.Such as here use, term N-vinylamide (being total to) polymkeric substance refers to the homopolymer that obtains through the polymerization of N-vinylamide monomers, the multipolymer that perhaps obtains through N-vinylamide monomers and other monomer polymerization.This (being total to) polymkeric substance water soluble also serves many purposes.
The example of comonomer comprises that (methyl) Acrylic Acid Monomer is like (methyl) vinylformic acid, its salt, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid (different) propyl ester, (methyl) Bing Xisuandingzhi, (methyl) Octyl acrylate, (methyl) 2-EHA, (methyl) vinylformic acid methoxyl group ethyl ester, (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester and polyalkylene oxide glycol list (methyl) propenoate; (methyl) acrylamide monomer is like (methyl) acrylic amide, N; N-dimethyl-(methyl) acrylic amide, N; N-diethylammonium (methyl) acrylic amide, N-methylol (methyl) acrylic amide, 2-(methyl) acrylic amide-2-methyl propane sulfonic acid and salt thereof, and N-sec.-propyl (methyl) acrylic amide; Vinyl ester monomers such as vinyl-acetic ester, vinyl butyrate and valeric acid vinyl acetate; Styrene monomer such as vinylbenzene, alpha-methyl styrene, p-methylstyrene, p-methoxystyrene and-chloro-styrene; Vinyl ether monomers such as methylvinylether, butyl vinyl ether and vinyl benzyl ether; Dicarboxylic acid monomer such as maleic anhydride, toxilic acid and salt thereof, fumaric acid and salt thereof, dimethyl maleate and DEF; Allyl monomer such as vinyl carbinol, allyl phenyl ether and allyl acetate; (methyl) vinyl cyanide, vinylchlorid, ethene and propylene.
Said comonomer can use separately or two or more are used in combination.The amount of comonomer can suitably determine according to the purposes of multipolymer, and is no more than 60 quality % ideally with respect to monomeric total amount, preferably is no more than 40 quality %.
< purposes of N-vinylamide (being total to) polymkeric substance >
Should have thickening and dispersion effect by (being total to) polymkeric substance, and be suitable for the field of broad range described below.
(1) industrial dispersion agent
Should can be used as dispersion agent inorganic and organic dust by (being total to) polymkeric substance.The example of powder comprises inorganic powder such as silicon-dioxide, aluminum oxide, titanium oxide and lime carbonate; Mineral powders such as talcum and kaolin; Pigment powder such as carbon black; Toner such as urethane, polyacrylic ester and Vilaterm; And organic dust such as stearate.Should these powder be scattered in polar solvent such as the water (being total to) polymkeric substance.
(2) be used for the thickening material and the dispersion agent of pigment and printing ink
Being somebody's turn to do (being total to) polymkeric substance can be as dispersion agent, viscosity modifier, levelling agent and the wetting agent of paint and printing ink.
(3) be used for water and oil handling agent and extraction agent
(4) makeup
Should can be used as emulsion stabilizer, lubricant and the emulsifying agent (being used for emulsification cosmetic) in makeup such as shampoo, amendment and the astringent by (being total to) polymkeric substance.Should can also be used for facial mask and setting agent by (being total to) polymkeric substance.
(5) toilet articles
This (being total to) polymkeric substance can be used as thickening material, toothpaste, sanitising agent, tenderizer and the industrial detergent of the liquid washing agent of (being used for garment material, kitchen, bathroom and ceramic tile).
(6) tackiness agent and tackiness agent auxiliary agent
(7) medicine
Should can be used to keep medicament and make medicament continue to discharge by (being total to) polymkeric substance.Particularly, find should (being total to) polymkeric substance between the base-material of tablet (slow releasing tablet), enteric coated tablet preparation, binder formulation such as paste and plaster, ointment, sustained release preparation, stomach internal buoyancy slow releasing tablet, mucous membrane preparation, tetter compsn (medical film), wound dressings, dental material, oral absorption agent and tooth, to have purposes aspect the cleaning material.(being total to) polymkeric substance also can be used for medical devices such as urethral catheter and enema as lubricant, and they heat in the sterilization autoclave and reuse, and also can be used as the viscosity modifier that is used for diagnostic reagent.
(8) water-absorbing material, water preservative, sealing agent and cold insulation body
(9) other
Should can be used as the release agent of papermaking treatment agent, air freshener, deodovization agent, siccative, fermentation assistant, wrapping material and old wallpaper by (being total to) polymkeric substance, and the dielectric substrate that is used for thickening material, single jersey material, ultrasonic crack detection contact medium, ultrasonic probe and the battery and the transmitter of toy.
The present invention will be described in more detail through following embodiment, in any case but should be interpreted as the present invention is not limited thereto.
[embodiment]
[embodiment 1]
Under 350 ℃ with N-(1-methoxy ethyl) ethanamide pyrolysis, and the evaporation low boiler cut to obtain thick N-vinyl acetamide (it contains 86.6 quality %N-vinyl acetamide, 3.5 quality % ethanamides and 9.4 quality %N-(1-methoxy ethyl) ethanamide).The N-vinyl acetamide that 50g is thick combines with 10g methyl alcohol, and with this mixture heating up to 50 ℃ so that this thick N-vinyl acetamide dissolving.Gained solution is combined with the 200g normal hexane, then be cooled to 10 ℃ so that crystal separate out.N-vinyl acetamide crystal be white and be shaped as sheet (scale), and separate out in mutually at the upper strata normal hexane.Remove the lower layer methanol phase, and through the filtered and recycled crystal.With crystals weighed is 20.6g, and purity is 98.7%.
[embodiment 2]
With N-(1-alkoxyethyl) ethanamide pyrolysis, the evaporation low boiler cut is to obtain thick N-ethanoyl ethanamide (it contains 85.2 quality %N-vinyl acetamide, 3.3 quality % ethanamides and 11.2 quality %N-(1-methoxy ethyl) ethanamide) under 330 ℃.With thick N-ethanoyl ethanamide such as embodiment 1 said the processing to produce N-vinyl acetamide crystal, it is weighed as 16.3g, and purity is 99.1%.
[embodiment 3]
Repeat the program of embodiment 1, difference is to replace normal hexane with sherwood oil.Therefore, N-vinyl acetamide crystal is separated out, its color is for white and be shaped as sheet, and separates out in mutually at the sherwood oil on upper strata.N-vinyl acetamide crystal is filtered, and do not separate methyl alcohol mutually with sherwood oil mutually.Clean this crystal with very small amount of cold methanol.The crystals weighed that obtains is 13.9g, and purity is 98.3%.
[Comparative Examples 1]
Trial is to carry out the purifying of N-vinyl acetamide with embodiment 1 identical mode, and difference is not add normal hexane.When crystallization not taking place down during the thick N-vinyl acetamide solution of cooling at 10 ℃.Crystallization is being no more than-5 ℃ and is taking place but cause whole system to be solidified and can not reclaim N-vinyl acetamide crystal through filtering to wait.
[Comparative Examples 2]
Trial is to carry out the purifying of N-vinyl acetamide with embodiment 1 identical mode, and difference is to replace 10g methyl alcohol to be used for this thick N-vinyl acetamide of dissolving the 200g normal hexane.Also do not dissolve even thick N-vinyl acetamide heats down at 50 ℃, the thick N-vinyl acetamide phase of fused and the normal hexane that contain impurity exist respectively mutually.Thereby, N-vinyl acetamide crystallization failure.
[embodiment 4]
High purity N-the vinyl acetamide that obtains among the 240g embodiment 1 is dissolved in the 160g pure water, then adds the 1.2g Thiovanic acid as chain-transfer agent.This solution is neutralized under pH9-10 with aqueous sodium hydroxide solution.Thereby preparation monomer solution.Through with 4.8g azo diradical polymerization starter 2; 2 '-azo two (2-methyl-propyl amidine) dihydrochloride (V-50; Wako Pure ChemicalIndustries; Ltd. make molecular weight: 271, can produce the radical material of 2 molar equivalents during cracking) be dissolved in the 395.2g pure water preparation initiator solution separately.This monomer solution is stored under being not more than 10 ℃ with the prevention polymerization.The 200g water of in the 1L flask of prolong, TM, whisking appliance and dropper is housed, packing into, and water heated in nitrogen gas stream under about 100 ℃ of backflows.This monomer solution and initiator solution are gone through dropwise adding simultaneously in about 1 hour, the polymerization of N-vinyl acetamide.This weight-average molecular weight of gathering (N-vinyl acetamide) is 45,000 through light scattering method measuring.The polymerizability of N-vinyl acetamide is with high as the disclosed N-vinyl acetamide that obtains through the pressure crystallization in patent documentation 4 and 5.
When not using above-mentioned specific pure and mild specific aliphatic hydrocrbon, can not get the product of purifying, perhaps the yield of purified product is low and impracticable.
Claims (4)
1. method for preparing high-purity N-vinylcarboxamides, it comprises:
(A) thick N-vinylamide is dissolved in the step in the alcohol with 1-3 carbon atom, this thick N-vinylamide contains the N-vinylamide of 50-97 quality %;
(B) aliphatic hydrocrbon that adding has 5-10 carbon atom in the compsn that in step (A), obtains is to separate out this N-vinylamide crystalline step; With
(C) the N-vinylamide crystalline step of separating out in the separating step (B);
Wherein in step (A), thick N-vinylamide is dissolved in 30-100 ℃ the alcohol with 1-3 carbon atom, in step (B), under-30 to 40 ℃, this N-vinylamide crystal is separated out; Wherein said N-vinylamide is the N-vinyl acetamide;
Wherein said thick N-vinylamide comprises being selected to have 5 or the impurity of alcohol, acid amides, N-(1-alkoxyethyl) acid amides and the ethylene diamide of carbon atom still less.
2. the method that described in claim 1, prepares high-purity N-vinylcarboxamides wherein in step (C), is passed through filtering separation with this N-vinylamide crystal.
3. described in claim 1, prepare the method for high-purity N-vinylcarboxamides, wherein said alcohol is methyl alcohol.
4. the method that described in claim 1, prepares high-purity N-vinylcarboxamides, wherein said aliphatic hydrocrbon are normal hexane and/or sherwood oil.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005233452 | 2005-08-11 | ||
| JP233452/2005 | 2005-08-11 | ||
| PCT/JP2006/315894 WO2007018279A1 (en) | 2005-08-11 | 2006-08-04 | Process for producing high-purity n-vinylcarboxamides |
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| Publication Number | Publication Date |
|---|---|
| CN101238093A CN101238093A (en) | 2008-08-06 |
| CN101238093B true CN101238093B (en) | 2012-05-30 |
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| CN2006800288648A Expired - Fee Related CN101238093B (en) | 2005-08-11 | 2006-08-04 | Process for producing high-purity N-vinylcarboxamides |
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| Country | Link |
|---|---|
| US (1) | US20090287020A1 (en) |
| EP (1) | EP1915336A4 (en) |
| KR (1) | KR100984601B1 (en) |
| CN (1) | CN101238093B (en) |
| TW (1) | TW200726738A (en) |
| WO (1) | WO2007018279A1 (en) |
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|---|---|---|---|---|
| JP5596562B2 (en) * | 2009-01-06 | 2014-09-24 | 昭和電工株式会社 | N- (1-hydroxyethyl) carboxylic acid amide compound and method for producing the same |
| WO2020110614A1 (en) * | 2018-11-29 | 2020-06-04 | 昭和電工株式会社 | Method for producing n-vinylcarboxylic amide |
| CN110183345A (en) * | 2019-06-13 | 2019-08-30 | 英德市云超聚合材料有限公司 | The purifying process and preparation process of a kind of N, N '-methylene-bisacrylamide |
| US20220220064A1 (en) * | 2019-12-26 | 2022-07-14 | Showa Denko K.K. | Method for producing highly polymerizable n-vinyl carboxylic acid amide monomer |
| CN113874349A (en) * | 2019-12-26 | 2021-12-31 | 昭和电工株式会社 | Method for producing highly polymerizable N-vinylcarboxylic acid amide monomer |
| CN113939497A (en) | 2019-12-26 | 2022-01-14 | 昭和电工株式会社 | Method for producing highly polymerizable N-vinylcarboxylic acid amide monomer |
| JPWO2021132365A1 (en) * | 2019-12-26 | 2021-07-01 | ||
| WO2021132363A1 (en) * | 2019-12-26 | 2021-07-01 | 昭和電工株式会社 | Method for manufacturing highly polymerizable n-vinyl carboxylic acid amide monomer |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510515A (en) * | 1993-09-21 | 1996-04-23 | Showa Denko K.K. | Process for purifying polar vinyl compound |
| CN1082943C (en) * | 1995-12-28 | 2002-04-17 | 昭和电工株式会社 | Highly polymerizable n-vinylcarboxylic acid mide and production process thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3938016A1 (en) * | 1988-11-18 | 1990-05-23 | Air Prod & Chem | N-vinyl acetamide purificn. to remove acet-amide by extn. - with aromatic hydrocarbon and conc. aq. salt soln. and use in polymer and poly-vinyl:amine prodn. |
| HU216137B (en) * | 1995-07-13 | 1999-04-28 | Showa Denko Kabushiki Kaisha | Polymerizable n-vinylcarboxylic acid amide, production and polymerization process thereof |
-
2006
- 2006-08-04 CN CN2006800288648A patent/CN101238093B/en not_active Expired - Fee Related
- 2006-08-04 EP EP06782680A patent/EP1915336A4/en not_active Withdrawn
- 2006-08-04 US US12/063,518 patent/US20090287020A1/en not_active Abandoned
- 2006-08-04 WO PCT/JP2006/315894 patent/WO2007018279A1/en active Application Filing
- 2006-08-04 KR KR1020087005775A patent/KR100984601B1/en not_active IP Right Cessation
- 2006-08-11 TW TW095129693A patent/TW200726738A/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5510515A (en) * | 1993-09-21 | 1996-04-23 | Showa Denko K.K. | Process for purifying polar vinyl compound |
| CN1082943C (en) * | 1995-12-28 | 2002-04-17 | 昭和电工株式会社 | Highly polymerizable n-vinylcarboxylic acid mide and production process thereof |
Non-Patent Citations (1)
| Title |
|---|
| masao murano et al..nuclear magnetic resonance spectra of poly(vinylamine),poly(N-vinylacetamide),and dimeric model compounds.《macromolecules》.1970,第三卷(第五期), * |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI375667B (en) | 2012-11-01 |
| KR100984601B1 (en) | 2010-09-30 |
| EP1915336A1 (en) | 2008-04-30 |
| WO2007018279A1 (en) | 2007-02-15 |
| CN101238093A (en) | 2008-08-06 |
| TW200726738A (en) | 2007-07-16 |
| US20090287020A1 (en) | 2009-11-19 |
| KR20080033535A (en) | 2008-04-16 |
| EP1915336A4 (en) | 2011-08-03 |
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